Environmentally friendly near-azeotropic mixed refrigerant

ABSTRACT

Disclosed is an environmentally friendly near-azeotropic mixed refrigerant, consisting essentially of HFO-1234 yf, HFE-143a and a third component, with the mass percentage of each component being: 70%-98% of HFO-1234yf, 1%-15% of HFE-143a and 1%-15% of the third component. The refrigerant of the present invention is environmentally friendly, excellent in thermodynamic properties, can directly realize drop-in substitution in an original system using HFC-134a without changing any parts, and can be used as a long term alternative to HFC-134a.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Continuation Application of U.S. patentapplication Ser. No. 16/924,894, filed Jul. 9, 2020, which is aDivisional Application of U.S. patent application Ser. No. 16/216,339,filed Dec. 11, 2018, which is a Divisional Application of U.S.application Ser. No. 14/899,944, filed on Dec. 18, 2015, which is anational stage application of PCT/CN2014/080384 filed Jun. 20, 2014 andChinese Patent Application No. 201310282218.6, filed Jul. 5, 2013, theentirety of all of which are incorporated by reference herein.

FIELD OF THE INVENTION

The present invention relates to a mixed refrigerant, in particular, toa refrigerant composition with extremely low greenhouse effect that candirectly be used as an alternative of HFC-134a without damage to theozone layer.

BACKGROUND OF THE INVENTION

1, 1, 1, 2-tetrafluoroethane (HFC-134a), as an alternative to CFC-12,has been widely used with its excellent performance. However, due to itshigh value of GWP up to 1430, it has been listed in one of therefrigerants with high GWP that are firstly eliminated in “KyotoProtocol”. For HFC-134a used in the small refrigeration equipments, mostof them have been substituted by HC-600a, while for the alternative toHFC-134a used in the industrial and commercial refrigeration andair-conditioning in cars, it has become a hot issue to be resolvedurgently across the world.

At present, internationally, the main alternatives to HFC-134a arecarbon dioxide (CO₂), 1, 1-difluoroethane (HFC-152a), 2, 3, 3,3-tetrafluoropropene (HFO-1234yf), etc. But they have their advantagesand disadvantages. CO₂ is environmentally friendly and non-combustible,but the system pressure is high, the energy efficiency is low, and thesystem should be re-designed with high costs. HFC-152a has a high energyefficient and low price of refrigerant, but its flammability is strongand it is necessary to add secondary loop, which causes a high costs.HFO-1234yf has low flammability, small system transformation but itsenergy inefficient is low and the cooling capacity is low. Therefore,the studies on the alternative to HFC-134a have been continuouslycarried out in various countries across the world, and mixed refrigerantis a major research field.

In the prior art, Patent Document CN1285699C (200410084844.5) disclosesa ternary composition composed of fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a) and 1, 1, 1, 2-tetrafluoroethane;CN101671542A (200910018489.4) discloses a mixture composed of 2, 3, 3,3-tetrafluoropropene (HFO-1234yf), 1, 1-difluoroethane (HFC-152a) andisobutene; CN101864277A (201010196224. 6) discloses a mixture composedof 2, 3, 3, 3-tetrafluoropropene (HFC-1234yf), 1, 1-difluoroethane(HFC-152a) and dimethyl ether (DME); CN102703033A (201210165277.0)discloses a mixture composed of 2, 3, 3, 3-tetrafluoropropene(HFC-1234yf), 1, 1, 1, 2-tetrafluoroethane (HFC-134a) and dimethyl ether(DME); CN102066518A (200980122002. 5) discloses a mixture composed of 2,3, 3, 3-tetrafluoropropene (HFC-1234yf), 1,1,1,2-tetrafluoroethane(HFC-134a) and 1, 1-difluoroethane (HFC-152a); CN102083935A(200980125796. 0) discloses a mixture composed of 1, 1, 1,2-tetrafluoroethane (HFC-134a) and 2, 3, 3, 3-tetrafluoropropene(HFC-1234yf). CN102083935A (200980125796. 0) discloses a mixturecomposed of 1, 1, 1, 2-tetrafluoroethane firing (HFC-134a) and 2, 3, 3,3-tetrafluoropropene (HFC-1234yf); and CN102712837A (201080038152. 0)discloses a mixture composed of 1, 1, 1, 2-tetrafluoroethane (HFC-134a),2, 3, 3, 3-tetrafluoropropene (HFC-1234yf) and difluoromethane (HFC-32).

The refrigerant compositions disclosed in the above patents have suchdrawbacks as high GWP value, strong flammability, high temperatureglide, low efficiency, small volume of cooling capacity, unable to bedirectly filled and used in HFC-134a system, etc. Therefore, it isnecessary to develop an alternative refrigerant of HFC-134a withexcellent cooling performance, better compatibility with existingsystems, and better environmental performance.

SUMMARY OF THE INVENTION

The object of the present invention is to provide an environmentallyfriendly near-azeotropic mixed refrigerant, which have more excellentenvironmental performance and use performance than HFC-134a. It can beused an alternative, low-cost refrigerant in the system using HFC-134awithout changing any parts.

In order to achieve the above object, the present invention adopts thefollowing technical solutions.

An environmentally friendly near-azeotropic mixed refrigerantessentially includes 2, 3, 3, 3-tetrafluoropropene (HFO-1234yf),trifluoro methyl ether(CF₃OCH₃, HFE-143a) and a third component, whereinthe third component is selected from one or two or more of fluoroethane(HFC-161), 1, 1, 1, 2-tetrafluoroethane (HFC-134a), difluoromethane(HFC-32), dimethyl ether (CH₃OCH₃, HFE-170), propane (HC-290),cyclopropane (C270) and their mass percentages of all components are asfollows:

HFO-1234yf: 70%-98%;

HFE-143a: 1%-15%;

The third component: 1%-15%.

When a third component is used for preparing the near-azeotropicrefrigerant as stated in the invention, any one or two or more thanthree of them can be selected as the third component from fluoroethane(HFC-161), 1, 1, 1, 2-tetrafluoroethane (HFC-134a), difluoromethane(HFC-32), dimethyl ether (CH₃OCH₃, HFE-170), propane (HC-290) andcyclopropane (C270), and when more than two substances are selected asthe third component, the mixed ratio is not specified.

For the environmentally friendly near-azeotropic mixed refrigerant inthe invention, the preferred mass percentage of various components is asfollows:

HFO-1234yf: 75%-94%;

HFE-143a: 5%-15%;

The third component: 1%-10%.

For the environmentally friendly near-azeotropic mixed refrigerant inthe invention, further, preferably the mass percentage of variouscomponents is as follows:

HFO-1234yf: 85%-94%;

HFE-143a: 5%-10%;

The third component: 1%-5%.

Preferably, the temperature glide of the environmentally friendlynear-azeotropic mixed refrigerant in the invention is less than 1° C.and the GWP value is less than 150. The present invention provides anenvironmentally friendly near-azeotropic mixed refrigerant suitable foralternative of HFC-134a, especially suitable for the alternative ofHFC-134a in automotive air conditioning. When it is used as alternativeof HFC-134a in automotive air conditioning, the automotive airconditioning system need not change any part and the mixed refrigerantcan be directly filled to replace HFC-134a. Compared with prior art, theenvironmentally friendly near-azeotropic mixed refrigerant in theinvention has the following advantages:

(1) Environmental performance is superior to HFC-134a, theozone-depleting potential ODP value is zero, and the global warmingpotential (GWP) value is dramatically reduced compared with HFC-134a;

(2) It is safe in use, with low flammability;

(3) The evaporating pressure, condensing pressure and pressure ratio,etc. are quite equivalent to HFC-134a, and the cooling capacity per unitvolume is higher than HFC-134a, with less temperature glide. The COPvalue is greater than HFC-134a, with low exhaust gas temperature, andexcellent performance;

(4) Without changing any part of the equipment, the refrigerant can beused in a system originally using HFC-134a. It is compatible with thepiping components of the originally used HFC-134a refrigeration system,and it can reduce the amount of filling, improve energy efficiency, saveresources and energy.

DETAILED DESCRIPTION OF THE EMBODIMENTS

In the present invention, the refrigerant is prepared through physicallymixing of 2, 3, 3, 3-tetrafluoropropene (HFO-1234yf), trifluoro methylether (CF₃OCH₃, HFE-143a) and one, two or three or more fromfluoroethane (HFC-161), 1, 1, 1, 2-tetrafluoroethane (HFC-134a),difluoromethane (HFC-32), dimethyl ether (CH₃OCH₃, HFE-170), propane(HC-290), cyclopropane (C270) according to appropriate mixing ratiosunder the liquid state.

The said 2, 3, 3, 3-tetrafluoropropene (HFO-1234yf) has a molecularformula CH₂CFCF₃, with a molecular weight of 114.04, standard boilingpoint of −29.35° C., critical temperature of 94.7° C., critical pressureof 3. 38 MPa, and GWP value of 4. The said trifluoro methyl ether(CF₃OCH₃, HFE-143a) has a molecular formula CF₃OCH₃, with a molecularweight of 100.04, standard boiling point of −24.0° C., criticaltemperature of 104.8° C., critical pressure of 3.59 MPa, and GWP valueof 750. The said fluoroethane (HFC-161) has a molecular formula CH₃CH₂F,with a molecular weight of 48.06, standard boiling point of −37.1° C.,critical temperature of 102. 2° C., critical pressure of 4. 7 Mpa, andGWP value of 12.

The said difluoromethane (HFC-32) has a molecular formula CH₂F₂, with amolecular weight 52.02, standard boiling point of −51. 7° C., criticaltemperature of 78.2° C., critical pressure of 5.78 MPa, and GWP value of675.

The said 1, 1, 1, 2-tetrafluoroethane (HFC-134a) has a molecular formulaCH₂FCF₃, with a molecular weight of 102.03, standard boiling point of−26.1° C., critical temperature of 101. 1° C., critical pressure of 4.06MPa, and GWP value of 1430. The said dimethyl ether (HFE-170) has amolecular formula CH₃OCH₃, with a molecular weight of 46.07, standardboiling point of −24. 8° C., critical temperature of 127. 2° C.,critical pressure of 5. 34 MPa, and GWP value of about 1. The saidpropane (HC-290) has a molecular formula CH₃CH₂CH₃, with a molecularweight of 44.10, standard boiling point of −42.1° C., criticaltemperature of 96.7° C., critical pressure of 4.25 MPa and GWP value ofabout 20.

The said cyclopropane (C-270) has a molecular formula CH₂CH₂CH₂, with amolecular weight of 42.08, standard boiling point of −31.5° C., criticaltemperature of 125. 2° C., critical pressure of 5.58 MPa, and GWP valueof about 20.

The following examples are illustrative of several embodiments of thepresent invention, but the invention is not limited to these specificembodiments. Technicians skilled in the art should be aware that thepresent invention encompasses all options, modifications and equivalentsas specified in the claims.

Example 1

Physically mix HFO-1234yf, HFE-143a and C270 in the liquid phaseaccording to a ratio of 70: 15: 15 (by mass percentage).

Example 2

Physically mix HFO-1234yf, HFE-143a and E170 in the liquid phaseaccording to a ratio of 75: 15: 10 (by mass percentage).

Example 3

Physically mix HFO-1234yf, HFE-143a and R134a in the liquid phaseaccording to a ratio of 80: 10: 5 (by mass percentage).

Example 4

Physically mix HFO-1234yf, HFE-143a and R290 in the liquid phaseaccording to a ratio of 90:5: 5 (by mass percentage).

Example 5

Physically mix HFO-1234yf, HFE-143a and R161 in the liquid phaseaccording to a ratio of 94: 1:5 (by mass percentage).

Example 6

Physically mix HFO-1234yf, HFE-143a and R32 in the liquid phaseaccording to a ratio of 98: 1:1 (by mass percentage).

The features and effects of the invention are described by comparing theperformance of above embodiment with HFC-134a.

1. Environmental Performance

The environmental performance of above embodiment is compared with thatof HFC-134a, as shown in table 1. For the ODP value, the value of CFC-11is used as the reference value 1. 0, for the GWP value, the value of CO₂is used as the reference value 1. 0 (100 years).

TABLE 1 Environmental performance Working medium ODP GWP Example 1 0 120Example 2 0 115 Example 3 0 150 Example 4 0 40 Example 5 0 15 Example 60 20 HFC-134a 0 1430

As shown from above table 1, the ODP value of the above embodiments iszero and the value of global warming potential (GWP) is 15˜150, all lessthan that of HFC-134a and in line with EU MAC Directive (GWP value: nogreater than 150). Its impact on the environment is much less thanHFC-134a, and the environmental performance is excellent, and it can beused as a long term alternative of HFC-134a.

2. Temperature Glide

TABLE 2 Temperature glide table Bubble point Dew point TemperatureWorking medium temperature (° C.) temperature (° C.) glide Example 1−31.30 −31.04 0.26 Example 2 −29.79 −29.71 0.08 Example 3 −30.53 −30.460.07 Example 4 −31.91 −31.08 0.83 Example 5 −31.65 −30.84 0.81 Example 6−32.28 −30.03 2.25

As shown from above table, except for the Example 6, the temperatureglide is less than 1° C., showing it is near-azeotropic mixture,facilitating the stable operation of the system.

3. Thermal Parameters and Thermodynamic Properties Under the automotiveair conditioning conditions (ie, evaporation temperature=−1.0° C.,condensing temperature=62. 0° C., intake air temperature=9° C.,supercooled temperature=57° C.), the thermal parameters (i.e.evaporation pressure P₀, condensing pressure P_(k), pressure ratioP_(k)/P₀, exhaust temperature t₂) and relative heat capacity (i.e.relative COP, the relative heat capacity per unit mass q₀, relativeheating capacity per unit volume q_(v), and relative power consumptionper unit volume w_(v)) of above embodiments and HFC-134a are shown intable 3.

The above relative thermodynamic property refers to the ratio ofthermodynamic property of various embodiments to that of HFC-134a, andthe relative density refers to the relative density of the liquid at 25°C.

TABLE 3 Comparison of thermal parameters and thermodynamic propertiesParameters P₀ P_(k) t₂ Relative Relative Relative Relative Unit MPa MPaP_(k)/P₀/ ° C. COP/ q₀/ q_(k)/ density/ Example 1 0.3251 1.7896 5.5075.3 1.07 1.12 1.07 0.82 Example 2 0.3101 1.7530 5.56 73.1 1.05 1.021.01 0.86 Example 3 0.3194 1.7992 5.63 70.2 1.01 0.81 1.02 0.90 Example4 0.3277 1.8037 5.50 69.4 1.01 0.83 1.04 0.85 Example 5 0.3264 1.81215.55 69.4 1.01 0.80 1.04 0.88 Example 6 0.3230 1.7844 5.52 67.9 1.010.74 1.01 0.90 HFC-134a 0.2823 1.7628 6.24 77.4 1 1 1 1

As shown from table 3, under the automotive air conditioning conditions,the condensing pressure of above embodiment is equivalent to that ofHFC-134a, but the pressure ratio and exhaust temperature are lower thanthose of HFC-134a, which can be directly filled in the original systemusing HFC-134a. The density of above embodiment is lower than that ofHFC-134a, which can reduce the filing amount of working medium. Thevolumetric cooling capacity of above embodiment is higher than that ofHFC-134a, having the energy-saving effect.

1. An environmentally friendly near-azeotropic mixed refrigerantessentially comprises HFO-1234yf, HFE-143a and a third component,wherein the third component is HFE-170, and their mass percentages ofall components are as follows: HFO-1234yf: 70%-98%; HFE-143a: 1%-15%;The third component: 1%-15%.
 2. The environmentally friendlynear-azeotropic mixed refrigerant according to claim 1, wherein the masspercentages of various components are as follows: HFO-1234yf: 75%-94%;HFE-143a: 5%-15%; The third component: 1%-10%.
 3. The environmentallyfriendly near-azeotropic mixed refrigerant according to claim 1, whereinthe mass percentages of various components are as follows: HFO-1234yf:85%-94%; HFE-143a: 5%-10%; The third component: 1%-5%.
 4. Theenvironmentally friendly near-azeotropic mixed refrigerant according toclaim 1, wherein the temperature glide of the refrigerant is less than1° C.
 5. The environmentally friendly near-azeotropic mixed refrigerantaccording to claim 1, wherein the GWP value of the refrigerant is lessthan
 150. 6. The environmentally friendly near-azeotropic mixedrefrigerant according to claim 1, wherein the refrigerant is used as analternative of HFC-134a.
 7. The environmentally friendly near-azeotropicmixed refrigerant according to claim 5, wherein the refrigerant is usedas an alternative of HFC-134a in the automotive air conditioning.
 8. Theenvironmentally friendly near-azeotropic mixed refrigerant according toclaim 6, wherein the automotive air conditioning system need not changeany part and the mixed refrigerant can be directly filled as analternative of HFC-134a.